CN107841008B - Easily-processed reinforced styrene butadiene rubber and preparation method thereof - Google Patents
Easily-processed reinforced styrene butadiene rubber and preparation method thereof Download PDFInfo
- Publication number
- CN107841008B CN107841008B CN201610835753.3A CN201610835753A CN107841008B CN 107841008 B CN107841008 B CN 107841008B CN 201610835753 A CN201610835753 A CN 201610835753A CN 107841008 B CN107841008 B CN 107841008B
- Authority
- CN
- China
- Prior art keywords
- butadiene rubber
- styrene
- reinforcing
- reinforcing agent
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 70
- 229920001971 elastomer Polymers 0.000 claims abstract description 62
- 239000005060 rubber Substances 0.000 claims abstract description 62
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005865 alkene metathesis reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims description 62
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- -1 thioamide compound Chemical class 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- IRTACFOVZDBFEX-UHFFFAOYSA-N ethenyl-diethoxy-ethylsilane Chemical compound CCO[Si](CC)(C=C)OCC IRTACFOVZDBFEX-UHFFFAOYSA-N 0.000 claims description 9
- KBIWOJBFYNSQKW-UHFFFAOYSA-N 3-ethenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=C)=C1C(O)=O KBIWOJBFYNSQKW-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- RNCZBYQGHGAXTP-UHFFFAOYSA-N ethenyl-hexyl-dipentoxysilane Chemical compound C(=C)[Si](CCCCCC)(OCCCCC)OCCCCC RNCZBYQGHGAXTP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 150000002832 nitroso derivatives Chemical group 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- MMILTFOIUWTZFM-UHFFFAOYSA-N 2-ethenoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC=C MMILTFOIUWTZFM-UHFFFAOYSA-N 0.000 claims description 2
- PGGMLBNYLZDCBN-UHFFFAOYSA-N 7-cyclohexyl-2-ethenyl-3-sulfanylideneisoindol-1-one Chemical compound C(=C)N1C(C=2C(C1=O)=C(C=CC=2)C1CCCCC1)=S PGGMLBNYLZDCBN-UHFFFAOYSA-N 0.000 claims description 2
- OLTTVMKWLZAVBQ-UHFFFAOYSA-N 7-cyclohexyl-2-prop-1-enyl-3-sulfanylideneisoindol-1-one Chemical compound C(=CC)N1C(C=2C(C1=O)=C(C=CC=2)C1CCCCC1)=S OLTTVMKWLZAVBQ-UHFFFAOYSA-N 0.000 claims description 2
- FSOOWVYTLGDBFZ-UHFFFAOYSA-N C(=C)(C)[SiH2]CC(OCCCC)OCCCC Chemical compound C(=C)(C)[SiH2]CC(OCCCC)OCCCC FSOOWVYTLGDBFZ-UHFFFAOYSA-N 0.000 claims description 2
- GLKXEWVWWWLALC-UHFFFAOYSA-N N(=O)N(C1=CC2=CC=CC=C2C=C1)C=CC1=CC=CC=C1 Chemical compound N(=O)N(C1=CC2=CC=CC=C2C=C1)C=CC1=CC=CC=C1 GLKXEWVWWWLALC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012327 Ruthenium complex Substances 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- BBZZUDQCNMQSSE-UHFFFAOYSA-L [Ru](Cl)Cl.C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1 Chemical compound [Ru](Cl)Cl.C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1 BBZZUDQCNMQSSE-UHFFFAOYSA-L 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 239000004902 Softening Agent Substances 0.000 abstract description 15
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 27
- 239000003570 air Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010692 aromatic oil Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 2
- MQBPUUJYMURCOU-UHFFFAOYSA-N ethenyl-dihexyl-pentoxysilane Chemical group C(=C)[Si](CCCCCC)(CCCCCC)OCCCCC MQBPUUJYMURCOU-UHFFFAOYSA-N 0.000 description 2
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/08—Depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C2019/09—Metathese
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an easily-processed reinforced styrene-butadiene rubber and a preparation method thereof. The reinforcing type softening agent is obtained by adding an olefin metathesis catalyst and a scorch-proof rubber reinforcing agent into styrene-butadiene rubber to react, and compared with base rubber, the easy-to-process reinforcing type styrene-butadiene rubber product has the advantages that the Mooney viscosity is reduced by 0.2-2.0 units/part, the tensile strength is improved by more than 0.1 MPa/part, and the scorch time is delayed by 1-15 s/part.
Description
Technical Field
The invention relates to styrene butadiene rubber and a preparation method thereof, in particular to reinforced easy-to-process styrene butadiene rubber and a preparation method thereof.
Background
The Mooney viscosity of the emulsion polymerized styrene-butadiene rubber raw rubber is generally 40-130M L1+4 100℃Mooney requirements for the mixes are generally below 90M L1+4 100℃(ii) a The raw rubber has lower strength, generally only 5.5 +/-0.5 MPa, and the strength is improved mainly by reinforcing agent in the post-processing process, generally reaching 21.5-24.5 MPa. The reinforcing agent mainly comprises inorganic powder such as carbon black, white carbon black, nano calcium carbonate and montmorillonite, the self-agglomeration of the inorganic powder is serious, and high energy is required for mixing the inorganic powder with rubber, and the inorganic powder is generally repeatedly kneaded and mixed for a long time on an open mill or an internal mixer. In the open milling or banburying process, a certain amount of softener is generally required to be added. Generally, the low molecular weight substances can provide a certain flexibility to the rubber compound, and can increase the plasticity, fluidity and adhesiveness of the rubber compound so as to facilitate the technological operations such as compression, molding and the like. And the dispersion of the powdery compounding agent is facilitated, the mixing temperature is reduced, and the processability of the rubber is improved.
The softener most used in rubber processing is a petroleum softener, and CN201410018005.7 provides a wet-skid resistant rubber softener and a preparation process, wherein the softener comprises the following raw materials in parts by weight: naphthenic oil: 70-90 parts of alkene mixed resin: 10-30 parts of aluminum trichloride: 0.1 to 1.0 portion. The anti-wet-skid rubber softener has the advantages of various performances of environment-friendly aromatic oil and environment-friendly naphthenic oil, and has good anti-wet-skid performance, lower rolling resistance and good wear resistance. CN201110345185.6 discloses a rubber softener and a preparation method thereof, which comprises the following raw materials in parts by weight: 10-30% of asphalt and 90-70% of naphthenic oil; the asphalt modified rubber softener is nontoxic and lower than European Union safety standards, fills up the blank of domestic production, and greatly saves the cost of domestic tire production enterprises. The softeners reported in the patent are actually physical plasticizers, mainly comprising aromatic oil, paraffin oil, naphthenic oil, heavy oil, paraffin, vaseline, asphalt, petroleum resin and the like, have only filling and softening effects on rubber, have no reinforcing effect, and are easy to separate out during the use of the product.
The Mooney scorch time of the styrene butadiene rubber can be used for measuring the scorch difficulty of the rubber material, and the longer the scorch time is, the less prone to the occurrence of the phenomenon of early vulcanization in the processing process. Scorch time can generally be measured by Mooney viscometer, the time required for the Mooney torque to reach 10%, denoted by T10, and the T10 of styrene butadiene rubber under standard test formulation is 2-3 min.
Disclosure of Invention
The invention aims to provide an easily-processed reinforced styrene butadiene rubber and a preparation method thereof, and particularly relates to a rubber prepared by adding a softening agent with a reinforcing function into styrene butadiene rubber in a rubber mixing process.
The easy-to-process reinforced styrene butadiene rubber comprises the following components in parts by mass: 100 parts of styrene-butadiene rubber and 1-100 parts of reinforcing softener, preferably 30-70 parts; the reinforced softener is prepared by the following method: styrene butadiene rubber is dissolved in a solvent to prepare a 1% w-50% w solution, preferably a 5% w-15% w solution, 0.1-1.0 part, preferably 0.1-0.3 part of olefin double decomposition catalyst and 1-50 parts, preferably 10-30 parts of scorch-proof rubber reinforcing agent are added into the solution based on 100 parts by mass of styrene butadiene rubber, air and water are isolated at 15-50 ℃ and preferably 20-30 ℃, the reaction is carried out for 0.5-5 hours, preferably 1-2 hours, and glue solution after the reaction is removed by the solvent to obtain the reinforcing type softening agent.
The scorch-proof rubber reinforcing agent is prepared by olefin double decomposition reaction of a scorch-proof agent and a reinforcing agent, wherein the scorch-proof agent is a nitroso compound containing an ethylenically unsaturated substituent, an organic acid or a thioamide; the reinforcing agent is an organic silane compound containing an ethylenically unsaturated substituent.
The specific preparation method of the scorch-proof rubber reinforcing agent comprises the following steps: the scorch retarder and the reinforcing agent are mixed in a ratio of 1: (0.1-5.0), preparing a solution with the mass concentration of 1% -30% by using a solvent, adding an olefin double decomposition catalyst accounting for 0.01-0.1% of the total mass of the anti-scorching agent and the reinforcing agent into the solution, isolating air and water, reacting at normal temperature for 0.5-8 h, and then removing the solvent by using a vacuum solvent removal device to prepare the anti-scorching rubber reinforcing agent.
The scorch retarder is nitroso compound containing ethylenically unsaturated substituent or organic acid or thioamide, and can be N-nitrosodi (vinyl benzene) amine, N-nitroso-styryl- β -naphthylamine, N-nitroso-2-propenyl-2, 4-dimethyl-1, 2-dihydroquinoline polymer, vinyl benzoic acid, vinyl salicylic acid, butenyl salicylic acid, vinyl phthalic acid, N-vinyl cyclohexyl thiophthalimide, N-propenyl cyclohexyl thiophthalimide, etc.;
the Mn of the reinforced softener prepared by the invention is 3000-100000.
The solvent is preferably a solvent which does not contain alkene in the structure and can dissolve styrene butadiene rubber; selected from hexane, cyclohexane, toluene, ethylbenzene, etc.
The reinforcing agent is an organic silane compound containing an ethylenically unsaturated substituent, and the structural formula of the reinforcing agent is as follows:
wherein:
R4-an aliphatic segment of an unsaturated olefin containing 2 to 18 carbon atoms, which may be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably vinyl;
R1、R3an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a siloxy group having 3 to 12 carbon atoms, and may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a n-hexyloxy group, a n-pentyloxy group, a n-heptyloxy group, an isooctyloxy group, a n-nonyloxy group, a phenoxy group, a chlorophenoxy group, an allyloxy group, a benzyloxy group, or a trimethylsiloxy group, preferably a methoxy group or an ethoxy group; r1And R3The purpose of the alkoxy group is to hydrolyze the alkoxy group by the action of heat and acid during the processing of styrene-butadiene rubber, thereby forming an-O-Si-space network structure in the rubber system and reinforcing the matrix rubber; if the organosilane has only one alkoxy group, it will form dimer after hydrolysis, and will not form-O-Si-space network structure, and will not play a role in reinforcement.
R2May be and R1The same group can also be a saturated chain segment containing 1-20 carbon atoms, a naphthenic group containing 3-8 carbon atoms or an aromatic group containing 6-8 carbon atoms; methyl, ethyl, methoxy, ethoxy are preferred.
The reinforcing agent of the present invention may be vinyltriethoxysilane, vinyldiethoxy-ethylsilane, vinyltrimethoxysilane, vinyldipentyloxy-hexylsilane, isopropenyldi-n-butoxyethylsilane, etc.
The olefin metathesis catalyst of the invention is a ruthenium carbene complex catalyst, which can be (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
And the like, preferably a metal carbene-based catalyst having an olefin metathesis function
The invention also provides a preparation method of the easy-to-process reinforced styrene butadiene rubber, which mainly comprises the following steps: the reinforcing type softening agent and the styrene butadiene rubber are mixed according to a proportion to prepare the easily processed reinforcing type styrene butadiene rubber.
The mixing can be carried out on an open mill or an internal mixer, and an open mill is preferably used.
The mixing process of the invention adopts the conventional mixing technology of rubber. The kneading temperature, the kneading time of the kneading frequency and the like are not particularly limited.
The invention also provides a preferable preparation method of the easy-processing styrene butadiene rubber, which comprises the following steps: firstly, mixing the styrene butadiene rubber on an open mill at 45-55 ℃ for 3-5 times, then adding the reinforcing type softening agent and mixing for 3-5 times to obtain the easily processed reinforcing type styrene butadiene rubber.
Compared with the base rubber, the easily-processed styrene-butadiene rubber prepared by the invention has the advantages that the Mooney viscosity is reduced by 0.2-2.0 units/part, the tensile strength is improved by more than 0.1 MPa/part, and the scorch time is delayed by 1-15 s/part by the addition of the softening agent.
The term "part" as used herein means a part by mass.
The invention is based on the technical principle that:
wherein n > m
The chemical reaction equation (1) takes vinyl benzoic acid as a scorch retarder and vinyl triethoxysilane as a reinforcing agent to carry out olefin double decomposition reaction to prepare the scorch retarder rubber reinforcing agent; the formula (2) is that the molecular weight of the styrene-butadiene rubber is reduced under the action of an olefin metathesis catalyst, and simultaneously reacts with the scorch-proof rubber reinforcing agent generated by the formula (1) to introduce a reinforcing group and a scorch-proof group on a side group.
The softener is a double decomposition reaction product of styrene butadiene rubber and a scorch-proof rubber reinforcing agent, has a similar composition with styrene butadiene rubber, and has a softening effect on rubber due to low molecular weight. Usually, the rubber processing formula adopts the operating oil as a softening agent, and small molecular aids such as a reinforcing agent, an anti-scorching agent and the like are added, and the aids are easily adsorbed to the surface by carbon black to reduce the action effect. This scheme will prevent burnt agent, reinforcer and softener chemical bonding, can effectively strengthen to prevent the scorching of rubber.
Detailed Description
The raw material auxiliaries required for the specific implementation of the invention are as follows:
(1) styrene butadiene rubber SBR1500, SBR1712, technical grade, langzhou petrochemical division;
(2) vinyltriethoxysilane, vinylethyldiethoxysilane, vinyltrimethoxysilane, reagent grade, Shanghai Virgillosiloxane GmbH;
(3) olefin metathesis catalyst:
ruthenium carbene catalyst, 500 mg/bottle, purity more than or equal to 98% w, Bailingwei science and technology Limited;
(4) hexane, cyclohexane, toluene, ethylbenzene, technical grade, langzhou petrochemical division;
(5) 2-vinylbenzoic acid, 3-vinylphthalic acid, reagent grade, gansu gacheng auxiliaries;
blending a softener with styrene butadiene rubber on an open mill, and testing the Mooney viscosity and the mechanical property of the raw rubber; the Mooney viscosity and the scorch time of the rubber are tested according to GB/T1232.1-2000, the mechanical property of the rubber is tested according to GB/T528-.
The parts are all parts by mass; the percentages are mass percentages.
Example 1:
mixing 2-vinylbenzoic acid serving as an anti-scorching agent and vinyltriethoxysilane serving as a reinforcing agent in a ratio of 1.0: 5.0 mol ratio, preparing a solution with 30 percent of mass concentration by using a hexane solvent, and adding 0.1 percent of olefin metathesis catalyst accounting for the total mass of the scorch retarder and the reinforcing agent into the solution
Isolating air and water, reacting at normal temperature for 8h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 1-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 1.1 percent concentration solution, and 0.15 part of olefin metathesis catalyst is added
And 1.3 parts of scorch-proof rubber reinforcing agent 1-1, isolating air and water at 15.5 ℃, reacting for 0.51 hour, removing glue solution after reaction through a solvent to obtain a reinforcing type softening agent, and measuring the Mn of the reinforcing type softening agent to be 90000.
100 parts of SBR1500 is mixed for 4 times at 75 ℃ on an open mill, 10 parts of the prepared reinforcing softener is added and mixed for 4 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 50 from 52, the tensile strength is improved to 26.3MPa from 25.3MPa, and the scorching time is improved to 189s from 125 s.
Comparative example 1:
compared with the example 1, the other conditions are the same, except that the scorch retarder is not added, specifically comprising the following steps: 100 parts of styrene butadiene rubber SBR1500 is dissolved in a hexane solvent to prepare a 1.1 percent solution, and 0.15 part of olefin metathesis catalyst is added
Air and water were cut off at 15.5 ℃ and reacted for 0.51 hour, and the reacted gum solution was removed by a solvent to obtain a softener, whose Mn was measured to be 96000.
100 parts of styrene butadiene rubber SBR1500 is mixed for 4 times at 75 ℃ on an open mill, 10 parts of the prepared reinforcing type softening agent is added and mixed for 4 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced from 52 to 50 through testing, the tensile strength is 25.2MPa, the Mooney viscosity is not improved, and the scorching time is as short as 90 s.
Example 2:
the scorch retarder 3-vinylphthalic acid and the reinforcing agent vinyldiethoxymethylsilane were mixed at a ratio of 1.0: mixing at 0.1 mol ratio, preparing into 1% solution with hexane solvent, adding antiscorching agent and reinforcementOlefin metathesis catalyst in an amount of 0.01% of the total mass
Isolating air and water, reacting at normal temperature for 0.5h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 2-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in toluene solvent to prepare 10 percent solution, and 0.9 part of olefin metathesis catalyst is added
And 48 parts of scorch-proof rubber reinforcing agent 2-1, isolating air and water at 49 ℃, reacting for 4.6 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring the Mn of the reinforcing type softener to be 3000.
And (2) uniformly mixing 100 parts of SBR (styrene butadiene rubber) 1500 and 14 parts of the prepared reinforcing softener on an open mill to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 32 from 52, the tensile strength is improved to 29.5MPa from 25.3MPa, and the scorching time is improved to 143s from 125 s.
Comparative example 2:
compared with example 2, the other conditions are the same, except that no olefin metathesis catalyst is added, specifically: the scorch retarder 3-vinylphthalic acid and the reinforcing agent vinyldiethoxymethylsilane were mixed at a ratio of 1.0: mixing the components in a molar ratio of 0.1, preparing a solution with the mass concentration of 1% by using a hexane solvent, isolating air and water, reacting at normal temperature for 0.5h, and removing the solvent by using a vacuum solvent removal device to prepare the scorch-proof rubber reinforcing agent 2-2.
100 parts of styrene butadiene rubber SBR1500 is dissolved in a toluene solvent to prepare a solution with the mass concentration of 10%, 48 parts of scorch-proof rubber reinforcing agent 2-2 is added, air and water are isolated at 49 ℃, the reaction is carried out for 4.6 hours, the glue solution after the reaction is removed through the solvent to obtain a reinforcing type softener product, and the Mn of the reinforcing type softener product is measured to be 170000.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 14 parts of the prepared reinforcing softener at 50 ℃ of an open mill, and the test shows that the Mooney viscosity is 52 without reduction, the tensile strength is improved from 25.3MPa to 26.5MPa, and the scorching time is improved from 125s to 129 s.
Example 3:
the scorch retarder 3-vinylphthalic acid and the reinforcing agent vinyltrimethoxysilane were mixed in a ratio of 1.0: 4.0 mol ratio, preparing 10% solution by mass with hexane solvent, adding 0.09% olefin metathesis catalyst of total amount of scorch retarder and strengthening agent into the solution
Isolating air and water, reacting at normal temperature for 4.5h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 3-1.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in cyclohexane solvent to prepare 25 percent solution, and 0.4 part of olefin metathesis catalyst is added
And 25 parts of scorch-proof rubber reinforcing agent 3-1, isolating air and water at 25 ℃, reacting for 2.5 hours, removing glue solution after reaction through a solvent to obtain a reinforcing softener product, and measuring the Mn of the reinforcing softener to be 60000.
And (2) uniformly mixing 100 parts of SBR1712 and 30 parts of the prepared reinforcing softener in an internal mixer to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 90 from 120, the tensile strength is improved to 27.5MPa from 26.3MPa, and the scorching time is improved to 212s from 125 s.
Comparative example 3:
compared with the example 3, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, specifically: and (2) adding 30 parts of high aromatic oil into 100 parts of styrene butadiene rubber SBR1712 in an internal mixer to obtain a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 80 from 120, the tensile strength is reduced to 23.5MPa from 26.3MPa, and the scorching time is 130 s.
Example 4:
2-vinylbenzoic acid serving as an anti-scorching agent and vinyl dipentyloxy-hexylsilane serving as a reinforcing agent are mixed in a ratio of 1.0: 3.0 mol% and 15% by mass of a hexane solventA concentrated solution to which is added 0.029% of the olefin metathesis catalyst based on the total amount of the scorch retarder and the strengthening agent
Isolating air and water, reacting at normal temperature for 4.8h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 4-1.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in a toluene solvent to prepare a 40 percent solution, and 0.5 part of olefin metathesis catalyst is added
And 10 parts of scorch-proof rubber reinforcing agent 4-1, isolating air and water at 15 ℃, reacting for 3 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring the Mn of the reinforcing type softener to be 40000.
100 parts of styrene butadiene rubber SBR1712 is mixed for 4 times at 60 ℃ on an open mill, 38 parts of the prepared reinforcing type softening agent is added for mixing for 5 times to prepare the easily processed reinforcing type styrene butadiene rubber, the Mooney viscosity is reduced to 60 from 120, the tensile strength is improved to 26.9MPa from 26.3MPa, and the scorching time is improved to 194s from 125 s.
Comparative example 4:
compared with the embodiment 4, the other conditions are the same, except that the reinforcing agent is vinyl pentoxy-dihexyl silane containing only one siloxane, specifically: 2-vinyl benzoic acid serving as an anti-scorching agent and vinyl pentoxy-dihexyl silane serving as a reinforcing agent are mixed in a ratio of 1.0: 3.0 mol ratio, preparing a solution with 15 percent of mass concentration by using a hexane solvent, and adding 0.029 percent of olefin metathesis catalyst accounting for the total mass of the scorch retarder and the reinforcing agent into the solution
Isolating air and water, reacting at normal temperature for 4.8h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 4-2.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in a toluene solvent to prepare a 40 percent solution, and 0.5 part of olefin is addedMetathesis catalysts
And 10 parts of scorch-proof rubber reinforcing agent 4-2, isolating air and water at 15 ℃, reacting for 3 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring the Mn of the reinforcing type softener to be 40000.
100 parts of styrene butadiene rubber SBR1712 is mixed for 4 times at 60 ℃ on an open mill, 38 parts of the reinforcing softener is added and mixed for 5 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 60 from 120, the tensile strength is improved to 26.4MPa from 26.3MPa through tests, no obvious change is caused, and the scorching time is improved to 196s from 125 s.
Example 5:
2-vinylbenzoic acid serving as a scorch retarder and vinyl ethyl diethoxysilane serving as a reinforcing agent are mixed in a proportion of 1.0: 3.7 mol ratio, preparing a solution with 19 mass percent by using a hexane solvent, and adding 0.05 percent of olefin metathesis catalyst accounting for the total mass of the scorch retarder and the reinforcing agent into the solution
Isolating air and water, reacting for 7h at normal temperature, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 5-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 30 percent solution, and 0.18 part of olefin metathesis catalyst is added
And 12 parts of scorch-proof rubber reinforcing agent 5-1, isolating air and water at 35 ℃, reacting for 4 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring Mn of the reinforcing type softener product to be 98000.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 95 parts of the prepared reinforcing softener on an open mill, and through tests, the Mooney viscosity is reduced to 32 from 52, the tensile strength is improved to 35.4MPa from 25.3MPa, and the scorching time is improved to 174s from 125 s.
Comparative example 5:
compared with the embodiment 5, the other conditions are the same, except that the reinforcing agent and the anti-scorching agent are added in the post-processing procedure, specifically: 100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 30 percent solution, and 0.18 part of olefin metathesis catalyst is added
Air and water were cut off at 35 ℃ and reacted for 4 hours, and the reacted gum solution was removed with a solvent to obtain a softener product, whose Mn was measured to be 101000.
100 parts of SBR1500 and 95 parts of the prepared softener, 12 parts of rubber reinforcing agent vinyl ethyl diethoxy silane and 12 parts of scorch retarder 2-vinyl benzoic acid which are relative to the mass of the softener are evenly mixed on an open mill to prepare a styrene butadiene rubber product, and through tests, the Mooney viscosity is reduced to 46 from 52, the tensile strength is improved to 25.4MPa from 25.3MPa, the strength is slightly improved, and the scorch time is improved to 134s from 125 s.
Example 6:
2-vinylbenzoic acid serving as a scorch retarder and vinyl ethyl diethoxysilane serving as a reinforcing agent are mixed in a proportion of 1.0: 4.5 mol ratio, preparing a solution with 25 percent mass concentration by using a hexane solvent, and adding 0.06 percent of olefin metathesis catalyst accounting for the total mass of the scorch retarder and the reinforcing agent into the solution
Isolating air and water, reacting for 4 hours at normal temperature, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 6-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in cyclohexane solvent to prepare 20 percent solution, and 0.9 part of olefin double decomposition catalyst is added
And 38 parts of scorch-proof rubber reinforcing agent 6-1, isolating air and water at 28 ℃, reacting for 3.2 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring the Mn of the reinforcing type softener to be 8000.
100 parts of styrene butadiene rubber SBR1500 is mixed for 3 times at 70 ℃ on an open mill, 1.1 part of the prepared reinforcing type softening agent is added for mixing for 5 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 50 from 52, the tensile strength is improved to 25.9MPa from 25.3MPa, and the scorching time is improved to 184s from 125 s. .
Comparative example 6:
compared with the example 6, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, and the strengthening agent and the scorch retarder are added, specifically: 100 parts of styrene butadiene rubber SBR1500 is mixed for 3 times at 70 ℃ on an open mill, 1.1 parts of high aromatic oil, 38 parts of rubber reinforcing agent vinyl ethyl diethoxysilane and 38 parts of scorch retarder 2-vinyl benzoic acid are added, and the mixture is mixed for 3 times at 70 ℃ on the open mill to prepare a styrene butadiene rubber product, through tests, the Mooney viscosity is reduced from 52 to 50, the tensile strength is not improved, and the scorch time is improved from 125s to 274 s.
Example 7:
mixing 2-vinylbenzoic acid as scorch retarder and vinyl ethyl diethoxysilane as reinforcing agent at molar ratio of 1.0: 3.5, preparing into 25% solution with hexane solvent, adding olefin metathesis catalyst 0.06% of the total amount of scorch retarder and reinforcing agent
Isolating air and water, reacting for 4h at normal temperature, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber reinforcing agent 7-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 18 percent solution, and 0.95 part of olefin metathesis catalyst is added
And 48 parts of scorch-proof rubber reinforcing agent 7-1, isolating air and water at 48 ℃, reacting for 3.2 hours, removing glue solution after reaction through a solvent to obtain a reinforcing type softener product, and measuring the Mn of the reinforcing type softener to be 7200.
And (2) uniformly mixing 100 parts of SBR (styrene butadiene rubber) 1500 and 70 parts of the prepared reinforcing softener in an internal mixer to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 39 from 52, the tensile strength is improved to 32.9MPa from 25.3MPa, and the scorching time is improved to 173s from 125 s.
Comparative example 7:
compared with the example 7, the other conditions are the same, except that the softening agent is added with the double decomposition catalyst for reaction firstly in the preparation process, then the reinforcing agent is added for reaction for a period of time, and then the scorch retarder is added for reaction for a period of time, specifically: 100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 18 percent solution, and 0.95 part of olefin metathesis catalyst is added
And (2) isolating air and water at 48 ℃ for reaction for 1h, adding 48 parts of rubber reinforcing agent vinyl ethyl diethoxysilane, isolating air and water at 48 ℃, reacting for 1.2 h, adding 10 parts of scorch retarder 2-vinylbenzoic acid, isolating air and water at 48 ℃, reacting for 1h, removing glue solution after reaction through a solvent to obtain a reinforcing softener product, and measuring the Mn of the reinforcing softener product to be 120000.
And (2) uniformly mixing 100 parts of SBR (styrene butadiene rubber) 1500 and 70 parts of the prepared reinforcing softener in an internal mixer to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 45 from 52, the tensile strength is improved to 27.9MPa from 25.3MPa, and the scorching time is improved to 144s from 125 s.
Claims (18)
1. An easily-processed reinforced styrene butadiene rubber comprises 100 parts of styrene butadiene rubber and 1-100 parts of a reinforced softener by mass, and is characterized in that the reinforced softener is prepared by the following method: dissolving styrene-butadiene rubber in a solvent to prepare a 1-50 w% solution, adding 0.1-1.0 part of olefin double decomposition catalyst and 1-50 parts of scorch-proof rubber reinforcing agent into the solution based on 100 parts by mass of styrene-butadiene rubber, isolating air and water at 15-50 ℃, reacting for 0.5-5 hours, and removing the reacted glue solution through the solvent to obtain a reinforcing softener; the scorch-proof rubber reinforcing agent is prepared by olefin double decomposition reaction of a scorch-proof agent and a reinforcing agent, wherein the scorch-proof agent is a nitroso compound containing an ethylenically unsaturated substituent, an organic acid or a thioamide compound; the reinforcing agent is an organic silane compound containing an ethylenically unsaturated substituent; the preparation method of the scorch-proof rubber reinforcing agent comprises the following steps: mixing the anti-scorching agent and the reinforcing agent according to the molar ratio of 1: 0.1-5.0, preparing a solution with the mass concentration of 1-30% by using a solvent, adding an olefin double decomposition catalyst accounting for 0.01-0.1% of the total mass of the anti-scorching agent and the reinforcing agent into the solution, isolating air and water, reacting for 0.5-8 h at normal temperature, and removing the solvent by using a vacuum solvent removal device to prepare the anti-scorching rubber reinforcing agent.
2. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein the content of the reinforcing softener is 30 to 70 parts by mass.
3. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein the styrene-butadiene rubber is dissolved in a solvent to prepare a solution having a concentration of 5 w% to 15 w%.
4. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein 0.1 to 0.3 part by mass of an olefin metathesis catalyst is added to 100 parts by mass of the rubber in the preparation of the reinforcing softener.
5. The easy-to-process reinforced styrene-butadiene rubber as claimed in claim 1, wherein 10 to 30 parts by mass of scorch retarder for rubber is added to 100 parts by mass of the rubber during the preparation of said reinforcing softener.
6. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein the solvent is a solvent capable of dissolving styrene-butadiene rubber without containing an olefin in its structure.
7. The easy-to-process reinforced styrene-butadiene rubber according to claim 1 or 6, wherein the solvent is selected from the group consisting of hexane, cyclohexane, toluene and ethylbenzene.
8. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein the scorch retarder is selected from the group consisting of N-nitrosodi (vinylbenzene) amine, N-nitroso-styryl- β -naphthylamine, N-nitroso-2-propenyl-2, 4-dimethyl-1, 2-dihydroquinoline polymer, vinylbenzoic acid, vinyl salicylic acid, butenyl salicylic acid, vinyl phthalic acid, N-vinylcyclohexyl thiophthalimide, and N-propenyl cyclohexylthiophthalimide.
9. The easy-to-process reinforced styrene butadiene rubber according to claim 1, wherein the reinforcing agent has the following structural formula:
wherein: r4Is an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms; r1、R3Is an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a siloxy group having 3 to 12 carbon atoms; r2Is a reaction with R1The same group, or a saturated chain segment containing 1-20 carbon atoms, a cycloalkyl containing 3-8 carbon atoms, or an aryl containing 6-8 carbon atoms.
10. The easy-to-process reinforced styrene-butadiene rubber as claimed in claim 9, wherein said R in said reinforcing agent formula4Selected from the group consisting of ethenyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylethenyl, 1-heptenyl, methacryloxypropyl, and methacryloxy.
11. The easy-to-process reinforced styrene-butadiene rubber as claimed in claim 9, wherein said R in said reinforcing agent formula1、R3Is selected from methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, n-hexyloxy, n-pentyloxy, n-heptyloxy, isooctyloxy, n-nonyloxy, phenoxy, chlorophenoxy, allyloxy, benzyloxy or trimethylsilyloxy.
12. The easy-to-process reinforced styrene-butadiene rubber as claimed in claim 9, wherein said R in said reinforcing agent formula2Selected from methyl, ethyl, methoxy or ethoxy.
13. The easy-to-process reinforced styrene butadiene rubber according to claim 9, wherein the reinforcing agent is selected from the group consisting of vinyltriethoxysilane, vinyldiethoxy-ethylsilane, vinyltrimethoxysilane, vinyldipentyloxy-hexylsilane and isopropenyldi-n-butoxyethylsilane.
14. The easy-to-process reinforced styrene-butadiene rubber according to claim 1, wherein the olefin metathesis catalyst is a metal carbene catalyst having an olefin metathesis function.
15. The easy-to-process reinforced styrene-butadiene rubber of claim 1, wherein the olefin metathesis catalyst is selected from the group consisting of (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
16. The method for preparing easily processed reinforced styrene-butadiene rubber according to claim 1, wherein the method mainly comprises mixing the reinforcing softener with styrene-butadiene rubber in proportion.
17. The method of preparing easily processed reinforced styrene-butadiene rubber according to claim 16, wherein said mixing is performed on a roll mill or an internal mixer.
18. The method of preparing easy-to-process reinforced styrene-butadiene rubber according to claim 16, comprising: the styrene butadiene rubber is firstly mixed for 3 to 5 times on an open mill at the temperature of between 45 and 55 ℃, and then the reinforced softener is added for mixing for 3 to 5 times to obtain the styrene butadiene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610835753.3A CN107841008B (en) | 2016-09-20 | 2016-09-20 | Easily-processed reinforced styrene butadiene rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610835753.3A CN107841008B (en) | 2016-09-20 | 2016-09-20 | Easily-processed reinforced styrene butadiene rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107841008A CN107841008A (en) | 2018-03-27 |
| CN107841008B true CN107841008B (en) | 2020-08-07 |
Family
ID=61656956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610835753.3A Active CN107841008B (en) | 2016-09-20 | 2016-09-20 | Easily-processed reinforced styrene butadiene rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107841008B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022181545A1 (en) * | 2021-02-24 | 2022-09-01 | 株式会社カネカ | Manufacturing method for polymer comprising hydrolyzable silyl group, and polymer, curable composition, and cured product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
| CN105732690A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Rubber reinforcing agent, preparation method thereof and preparation method of styrene butadiene rubber |
-
2016
- 2016-09-20 CN CN201610835753.3A patent/CN107841008B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
| CN105732690A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Rubber reinforcing agent, preparation method thereof and preparation method of styrene butadiene rubber |
Non-Patent Citations (1)
| Title |
|---|
| 用复分解催化剂促进橡胶化学反应;粷谷信三;《橡胶参考资料》;19881126(第11期);第31-37页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107841008A (en) | 2018-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3393824B1 (en) | Tyre for vehicle wheels | |
| US7312271B2 (en) | Solution masterbatch process using fine particle silica for low hysteresis rubber | |
| TWI478972B (en) | Free-flowing filler composition and rubber composition containing same | |
| EP1130053B1 (en) | Preparation of reinforced elastomer, elastomer composite and tire having component thereof | |
| GB2026499A (en) | Process for the preparation of a pulverulent filled rubber | |
| WO2010144890A2 (en) | Tires and tread formed from phenol-aromatic-terpene resin | |
| CN1141311A (en) | Silica reinforced rubber prepn. and tire with tread thereof | |
| CN102382338A (en) | Isoprene rubber blend and its preparation method | |
| JP5640269B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
| CN107429005A (en) | Rubber composition and pneumatic tire | |
| CN104650400B (en) | Cyclopentadiene-modified carbon nanotube/rubber composite material and preparation method thereof | |
| CN107841008B (en) | Easily-processed reinforced styrene butadiene rubber and preparation method thereof | |
| JP7019818B2 (en) | A functionalized polymer, a process for preparing the functionalized polymer, and a rubber composition containing the functionalized polymer. | |
| US9133281B2 (en) | Preparation and use of functionalized elastomers in rubber compositions containing silica filler and tire components thereof | |
| CN107841010B (en) | Preparation method of easy-to-process reinforced styrene butadiene rubber | |
| US6800126B2 (en) | Preparation and use of composite of rubber and carbon black aggregates and articles of manufacture, including tires, having a component comprised thereof | |
| CN107840903B (en) | Preparation method of reinforced softener for styrene butadiene rubber | |
| CN107841005B (en) | Easily-processed reinforced nitrile rubber and preparation method thereof | |
| CN107841007B (en) | Preparation method of easily processed reinforced nitrile rubber | |
| CN115160657B (en) | Rubber masterbatch and preparation method thereof | |
| CN104151650A (en) | Rubber composition containing modified rubber | |
| CN107840902B (en) | Preparation method of reinforcing plasticizer for nitrile rubber | |
| CN107841009B (en) | Easily-processed anti-aging styrene butadiene rubber and preparation method thereof | |
| WO2014090966A2 (en) | Rubber composition comprising an epoxy resin and a metal oxide which is different from zinc oxide | |
| CN107841011B (en) | Preparation method of easily-processed anti-aging styrene butadiene rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |